Production of hydrocarbons



Patented Apr. 21, 1931 UNITED STATES PATENT OFFICE RUDOLF WIETZEL, OF LUDWIGSEAIEN-ON-THE-BHINE, AN D KURT FISCHER, OF LE'UNA, GERMANY, ASSIGNORS, BY MESNE ASSIGNMENTS, TO STANDARD-I. G. COMPANY, OF LINDEN, NEW JERSEY, A CORPORATION OF DELAWARE rnonuc'rron or nrnnocnnnons Ho Drawing. Application filed August 17, 1928, Serial No.-800,381, and in Germany September 30, 1927.

This invention relates to improvements in the manufacture and production. of hydrocarbons by treating oxids of carbon with hydrogen or gases rich in hydrogen. I

It is already known that various hydrocarbons and other organic compounds can be obtained by treating oxids of carbon with hydrogen, or gases rich in hydrogen such as methane, at an elevated temperature and under suitable pressures, in the presence of catalysts. A large number of catalysts have already been proposed, especially activated iron, nickel and cobalt. It is already known that it is advantageous, according to the said process, to add alkalies to the catalysts.

We have now found that, in order to obtain, according to the said process, continuous high yields of hydrocarbons with more than one carbon atom, especially liquid hydrocarbons, it is a matter of decisive importance that the catalysts employed should contain, in addition to a metal 0 group 8 of the periodic system, in particular a metal of the iron group, a definite quantity of alkali compounds, namely less than about 0.6, and preferably between 0.4 and 0.6 part by weight of alkali, reckoned as alkali metal, per 100 parts by weight of the metal of the 8th group of the periodic system. In order to obtain good yields, it is also essential that the metal should be employed in a finely divided state and not in compact metallic form.

The catalysts may be prepared in a great variety of ways. Ferric oxid, which is completely free from alkali, precipitated, for example, with ammonia, may be employed, the suitable amount of. an alkali compound being subsequently added. Again, metals of group 8 may be precipitated by alkalies, and the precipitateswashed until the requisite rop'ort-ion of alkali is contained therein.

oreover, the very finely divided metals, obtained for example b decomposing metal carbonyls, may be actlvated with suitable amounts of dilute solutions of alkali compounds. The metals of group 8 may be employed singly or mixed together, and also, if desired, in conjunction with other substances such as copper, silver, gold, oxids of the alkaline earths, and thelike. The alkaii metal compounds may be employed in a great variety of forms, such as hydroxide,

carbonates, nitrates, chlorids, ferrocyanids,

formates, acetates, oxalates, and the like.

The methods of working already known in the catalytic synthesis of compounds from gases, particularly from carbon monoxid and hydrogen, such for example as work 111g n a cycle, the preliminary purification of the gases, the employment of preliminary catalysts arranged in front of the main catalyst, devices for removing the heat of the reaction, the separation of the reaction prodacts by washing, cooling or with adsorptlon masses, purifying the circulating gases and the like methods, may also be employed according to the present invention. Furthermore, the portions of the apparatus which become heated during the process and come into contact with the gases, may be constructed of silver, copper, manganese bronze, chr0- mium-nickel, aluminium, iron alloys such as chromium, tungsten or manganese steels, ferrosllicon or the like, or of iron which is provided with a coating adapted to resist the aotlon of the gases and in particular of carbon monoxid.

A great variety of mixtures containing hydrogen, oxids of carbon and the like may be employed as the initial materials, as for example water gas, coke oven gas, coal gas, producer gas, or mixtures of the same, with, if desired, the addition of carbon monoxid, hydrogen or other gases. The relative proportions in which the oxids of carbon on the one hand, and the hydrogen or/and hydrocarbons rich in hydrogen on the other, may exist in the aseous mixture, may vary considerably. or example, equal volumes of hydrogen and the oxids of carbon may be present in the gases, or the proportions of the oxids of carbon may be higher or lower. In some cases it is specially advantageous to employ gaseous mixtures in which the oxids of carbon constitute less than 25 per cent of the hydrogen and/or hydrocarbons rich in hydrogen present. In this case the reaction proceeds with particular ease.

The temperature employed usually ranges between about 225 and 375 C. and very good results are obtained at tem eratures of between about 260 and 280 The ressure to be ap lied may vary within wide limits, and there ore the work may be conducted at ordinary pressure, medium pressures, say about 20 or 50 atmospheres, and

also very high pressures such as 100 to 200 or even 1000 atmospheres and. more. The reaction space may be smaller in proportion as the pressure is higher. The deposition of the reaction products occurs with particular ease at elevated pressures. Generally s eaking the composition of the reaction pro uct varies according to the catalyst employed in each case. When the content of the catalyst in alkali is low, the low boiling hydrocarbons preponderate, whilst with a higher limit of alkali content there is geuer; I an increased tendency to the formation. 0 gher molecular products. In some the formation of hydrocarbons is accompanied by the formation of oxygen compounds, such for example as substances of character, acids of high molecular Wei; cohols and the like. If the alkaii core below about 003 part by weight of a al per 100 parts of metal of group 8 o I c periodic sy tem, the yields are lower: 1 he alkali content exceeds the limit of ch '0 06 part by "00 parts by -..talyst reach "he deposition The followi" trate the nature of however not limited tliercooi 11- sample l Washed.

100 parts by Weight of t The resulting catalyst. then charged into the rose .on a single passage of 'l or taining 25 per cent oi. 4 per cent of N and 1 U at 250 C. and under a mospheres, 10 cubic cent. lyst furnish 20 cubic c i carbons (benzine) which are nary temperature. Moreover, about 10 C. below zero, cubic centimeters of liquid hydrocarbons (liquid at ordinary temperature) containing more than 1 carbon atom, can be recovered A similar effect is produced by a catalyst containing; 10 parts of palladium and Oil. part of per 100 parts of iron.

or toe cataoi hydroud at ordibed with A mixture, precipitated with potassium hydroxid or potassium carbonate and containing iron, cobalt and uranium in the proportions 4: 2: 1, isrepeatedly decanted and washed with distilled water until its alkali content amounts to 0.17 part by weight of potassium per 100 parts by Weight of the metals of group 8. The mixture is dried at 200 C.

100 cubic centimeters of the catalyst prepared in this manner furnish, by a single passage of 1 cubic meter of a gas containin about 35 per cent of CO and per cent 0 H at a reaction temperature of 27 0 C. and under atmospheric pressure, 27 cubic centimeters of benzine and 5 cubic centimeters of liquefied gaseous hydrocarbons.

In the preparation of the catalyst, the decrease of the alkali content in Washing is continuously supervised. h drying and analyzing samples. If the slliali content oi the catalyst amounts to only 0.2 part by Weight of potassium, per 100 parts by Weight of metals of group 8, yield of benzine is only small, Whilst with an excessive content of alkali, such as 1.5 parts by Weight of potassium per 100 by Weight of met sis of group 8, the yield oi bensine hydro-- carbons diminishes in favor of higher molec ular products Moreover, the surface of the catalyst becomes coated with solid substances and the catalyst 1 store soon becomes inactive. Similar eficcts obtained with the following" catalysts ,00 parts of iron, 10 of cobalt end 02 part of potassium, or

" iron, 20

as, precipicaroonn, co'i'ialt and silver L, 1 by Weight, is decant- 0 often possible, o200 Theprod d is repeatdistilled again ir-egncted with a 111; c bonate to and c in the prope ed with edly well e water, dui r dried at 200 C, solution of sufficient po bring its alkali center of potassium per 100 by Weight of metals of the iron group. "ii "til a single passage of 1 cubic meter of a gas containing about 25 per cent of C0 and about per cent of 4 per cent of N, and 1 per cent of methane, at about 290 C. and under a pressure of 50 atmospheres, 30 cubic centimeters of the above catalyst furnish 2a cubic Ewample 4 A mixture of alkali free, freshly recipitated h droxids of iron, cobalt and arium,

containmg the said metals in the proportions of 100: 10: 1 by weight, is intimately stirred with a solution of suificient rubidium hydroxid to introduce 0.18 part by weight of rubidium per 100 parts by weight of the metals of group 8. If the resulting catalyst be employed under the conditions specified in Example 3, but at about 275 C. a single passage of the gaseous mixture furnishes 3 grams'of a body resembling paraffin wax, 17 cubic centimeters o1 benzine and 5 cubic centimeters of liquefied hydrocarbon gases.

Ewample 5 about 260 (1., 150 cubic centimeters of the above catalyst furnish about 50 cubic centimeters of hydrocarbons with more than 1 carbon atom which are liquid at ordinary temperature, and 5 cubic centimeters of hydrocarbons with more than 1 carbon atom to be liquefied at low temperature.

Ew'ample 6 The wet mixture of the hydroxids of iron and cobalt precipitated with ammonia and containing the said metals in the proportions of 4 gram atoms of iron to 1 gram atom of cobalt, is well decanted, filtered by suction, washed, and dried at 150 to 200 C. The highly porous product is impregnated with a suflicient amount of a solution of sodium carbonate for it to contain, when re-dried, 0.44 part by weight of sodium per 100 parts by weight of metals of group 8. With a single passage of 1 cubic meter of gas containing about 25 per cent of CO and 75 per cent of H at 270 C. and under ordinary pressure, 200 cubic centimeters of this catalyst furnish 38 cubic centimeters of hydrocarbons liquid at ordinary temperature, and

1.2 liters of gaseous hydrocarbons, both products containing more than 1 atom of carbon in the molecule.

' What we claim is 1. In the production of hydrocarbons with more than one carbon atom in the molecule, by treating oxide of carbon with a gas comprising hydrogen, the step of carrying out.

the said treatment in the presence of a catalyst containing in addition to a metal of of the perlodic system a quantity of an alkali metal equivalent to from 0.4 to 0.6 part by weight of alkali reckoned as alkali metal per 100 parts by weight of the metal of the 8th group of the periodic system.

3. In the production of hydrocarbons with more than one carbon atom in the molecule, by treating oxids of carbon with a gas comprising hydrogen at temperatures ranging b tween about 225 and 375 (1, the step of arrying out the said treatment in the presence of a catalyst containing in addition to a metal of group 8 of the periodic system a quantity of an alkali metal compound equivalent to less than about 0.6 part by weight of alkali reckoned as alkali metal per 100 parts by weight of the metal of the 8th group of the periodic system.

4. In the production of hydrocarbons with more than one carbon atom in the molecule, by treating oxids of carbon with a gas comprising hydrogen at temperatures ranging between about 225 and 375 (1., the step of carrying out the said treatment in the presence of a catalyst containing in addition to a metal of group 8 of the periodic system a quantity of an alkali metal compound equivalent to from 0.4 to 0.6 part by weight of alkali reckoned as alkali metal per 100- parts by weight of the metal of the 8th group of the periodic system.

5. In the production of hydrocarbons with more than one carbon atom in the molecule,

by treating oxids of carbon with a gas comprising hydrogen, the step of carrying out the said treatment in the presence of a catalyst containing a metal of the iron group and a quantity of an alkali metal compound equivalent to less than about 0.6 part by weight of alkali reckoned as alkali metal per 100 parts by weight of the metal of thetiron group.

6. In the production of hydrocarbons with more than one carbon atom in the molecule, by treating oxids of carbon with a gas comprising hydrogen, the step of carrying out the said treatment in the presence of a catalyst containing a metal of the iron group and a quantity of alkali equivalent to from 0.4 to 0.6 part by weight of alkali reckoned as alkali 4 I 1, ao1,asa

metal per parts by weight of metal of the iron cup.

7 n the production of hydrocarbons with more than one carbon atom in the molecule, by treating oxids of carbon with a gas comrising h drogen at temperatures r'angin etween about 225 and. 375 0., the step 0 carrying out the said treatment in the resence of a catal st containing a metal 0 the iron group an a quantity of alkali equivalent to from 0.4 to 05 part by weight of alkali reckoned as alkali metal per 100 parts. by weight of metalof the iron group-n.

8. In the production of hydrocarbons with more than one carbon atom in the molecule, by treating oxids of carbon with a gas com prising hydrogen at temperatures ranging be tween about 225 and. 375 (5., the step of carrying out the said treatment in the presence of a catalyst containing e of iron and aii equivalent Weight of alkali 6C parts b to from. 0.4 to 0.6 pert reckoned. as alkali weight of the said met 9. process for the carbons with "more the the moiccuie, which. c: mixture containing ZLiJOC. i hon mono-Kid and per ce about 270 C. with a f T and cobalt in the propel atoms of iron to 1 0. 14 part of a soc nod. sodium per 1051 pa ie iron roup.

10 In the prod" bons by treating oi drogen at temperatn.. and 375 the step treatment in t e taming innit i. of the periodic eye e metal compound e part by weight of; metal 100 parts the 8th group of i 11. In the prod bone by treating oi drogen at teinpe about 2535" and out the said catalyst con and qnant" 0A to 6.6 part by i. as alkali metal per 10 metal of the iron 12. In the prodnci home by treating oxides c, to drogen at temperatures ranging between about 225 and 375 C., the step oi carrying out the said treatment in the presence of a catalyst containing a mixture of iron and cobalt and a quantity of u, a i equivalent to from 0.4 to 0.6 part by wei ht alkali reckoned as alkali metal er 100 parts by our hands.

RUDOLF WIETZEL. KURT FISCHER. 

